The hydrogenolysis of chlorofluoroethanes is a reaction which has been known for a long time (Patent GB 698,386), and many improvements have been made to it. There may be mentioned, for example, Patent GB 931,643, which employs a chromium oxide catalyst on an alumina support for the hydrogenolysis of 1,1,2-trichloro-1,2,2-trifluoroethane (F113) at temperatures in the region of 500.degree. C., and U.S. Pat. No. 3,636,173, which recommends for the hydrogenolysis of fluorohalocarbons a catalyst based on nickel or chromium on an alumina support activated beforehand with hydrofluoric acid. However, the catalytic compositions described in these patents necessitate high operating temperatures (from 300.degree. to 600.degree. C.) and the degrees of conversion or selectivities are low.
More recently, Patent EP 53,657 describes a process for the dehydrochlorination of F113 to chlorotrifluoroethylene (F1113) and trifluoroethylene (F1123) by means of a catalyst comprising a platinum group metal deposited on an alkaline magnesium fluoride type support. The results show a rapid deactivation of this catalyst with a substantial formation of 1,1,2-trifluoroethane (F143) and 1-chloro-1,2,2-trifluoroethane (F133) as by-products, even with low degrees of conversion of F113.
In Patent EP 355,907, a catalyst is described comprising an oxygenated porous support impregnated with a group VIII metal and a salt of an alkali metal or alkaline earth metal. The examples given show degrees of conversion of F113 of the order of 50% and selectivities for F1113 and F1123 which do not exceed 80%.
It is known, moreover, that catalysts based on copper alone are active in the hydrogenolysis of chlorofluoroalkanes. In U.S. Pat. No. 2,615,925, which employs such a catalyst, the operating temperatures are high (above 500.degree. C.) and the degrees of conversion and yields are mediocre.
It is also known that catalysts based on palladium are active. However, U.S. Pat. No. 4,876,405 shows that the use of such a catalyst in the hydrogenolysis of symmetrical difluorotetrachloroethane (F112) and of F113 leads to a substantial formation (more than 10%) of saturated by-products such as 1,1-difluoroethane (F152a) and 1,1,2-trifluoroethane (F143).
Moreover, the use of mixed catalysts has already been proposed. There may be mentioned U.S. Pat. No. 2,864,873 relating to mixed catalysts based on copper and on nickel on a chromium oxide support. These catalysts, which function at temperatures from 325.degree. to 425.degree. C., lead to degrees of conversion of F113 to F1113 of less than 50%. U.S. Pat. No. 2,697,124 relating to a copper/cobalt mixed catalyst on a magnesium fluoride support may also be mentioned; despite high temperatures (above 400.degree. C.) for the hydrogenolysis of F113, this catalyst gives degrees of conversion of F113 of less than 80%. The hydrogenolysis of F113 and of F114 with mixed catalysts based on copper and on chromium is also described in Patents BE 653,362 and FR 1,409,109; the operating temperatures are high, and the degrees of conversion and the yields of ethylenic compounds are low. The same applies to U.S. Pat. No. 3,505,417, which describes the hydrogenolysis of F114 to tetrafluoroethylene on copper/chromium or copper/cobalt catalysts.
It has now been found that, for the hydrogenolysis of chlorofluoroethanes or of chlorofluoroethylenes, the use of mixed catalysts based on copper or silver and on at least one platinum group metal (ruthenium, rhodium, palladium, osmium, iridium or platinum) enables excellent degrees of conversion and selectivities to be obtained at low operating temperatures.